DE3524629A1 - Zinc and copper complex salts of ethylenebisdithiocarbamic acid and of methyl N-(2-benzimidazolyl)carbamate, and process for the preparation and the use thereof - Google Patents

Abstract

The present invention relates to novel compounds, namely zinc and copper complex salts of ethylenebisdithiocarbamic acid and of methyl N-(2-benzimidazolyl)carbamate. <??>According to the invention, novel compounds, namely zinc and copper complex salts of ethylenebisdithiocarbamic acid and of methyl N-(2-benzimidazolyl)carbamate of the general formula <IMAGE> are proposed, in which M represents zinc if n = 1 or 2 or represents copper if n = 1. <??>The process for the preparation of the abovementioned compounds comprises reacting the copper chloride or zinc chloride with methyl N-(2-benzimidazolyl)carbamate in an aqueous medium at a temperature between 20 and 90 DEG C followed by the addition of sodium ethylenebisdithiocarbamate, and isolating the end product. <??>Fungicidal mixture which contains a filler and, as active ingredient, zinc and copper complex salts of ethylenebisdithiocarbamic acid and of methyl N-(2-benzimidazolyl)carbamate at a ratio (in % by weight) of: Active ingredient 0.01 to 99.5 Filler to 100

Description

The present invention relates to new chemical Compounds, namely on zinc and copper complex salts of Ethylene bis-dithiocarbamic acid and N- (benzimidazolyl- 2) -carbamic acid methyl ester, to a process their manufacture and for use as a fungiziede in the Agriculture and as antiseptics for non-metallic Materials.

Benzimidazole derivatives are known to be highly effective Preparations for fighting fungi Erysiphales from represent different cultures, but against fungi Peronosporales are not effective (US-PS 36 57 443, Cl. 424-273).

It is further known that fungicides from the class of Dithiocarbamates are active against fungi Peronosporales, but do not act on the mushrooms Erysiphales (N.N. Melnikov, "Chemistry and technology of pesticides", Moscow, publisher Chimÿa, 1974, N.N. Melnikov, Chimÿa i technologia Pesticidov, Moskva, isdatel'stvo Chimÿa, 1974).

Also known are complex salts of alkyl esters of N- (benzimidazolyl-2) -carbamic acid of the general formula where R is lower alkyl, M is zinc, copper, X is chlorine, bromine, acetate or propionate (DE-PS 19 57 712, cl. C07F, published in 1970).

The specified connections are insufficient antifungal activity.

The proposed new compounds, zinc and copper complex salts ethylene-bis-dithiocarbamic acid and  N- (Benzimidazolyl-2) -carbamic acid methyl ester have been newly developed and not described in the specialist literature.

The invention has for its object such new Compounds, zinc and copper complex salts of ethylene bis dithiocarbamic acid and the N- (benzimidazolyl-2) -carbamic acid methyl ester to produce which is a stronger fungicidal Have activity and a broader spectrum of activity.

This object is achieved in that, according to the invention, new substances, zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2) -carbamic acid methyl ester of the general formula be proposed in which M stands for zinc, when n = 1 or 2 or for copper when n = 1.

According to the invention, the following compounds are specifically proposed:
[N- (Benzimidazolyl-2) -O-methylcarbamato] zinc-ethylene bis-dithiocarbamate (Compound 1) of the formula [N- (Benzimidazolyl-2) -O-methylcarbamato] copper (II) - ethylene bis-dithiocarbamate (Compound 2) of the formula Di [N- (benzimidazolyl-2) -O-methylcarbamato] zinc-ethylene bis-dithiocarbamate (Compound 3) of the formula

According to the invention, a method for Preparation of the above compounds by reaction of copper chloride or zinc chloride with the methyl ester of N- (Benzimidazolyl-2) carbamic acid at a between 20 and 90 ° C temperature in an aqueous medium and then adding the aqueous solution of sodium ethylene bis-dithiocarbamate and isolating the end product in itself proposed in a known manner.

According to the invention, a fungicidal mixture is further proposed which contains zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2) -carbamic acid methyl ester as the active ingredient with the following ratio in mass% between the constituents mentioned:
Active ingredient 0.01. . . 99.5
Filler up to 100.0

The new compounds are powdered substances that are insoluble in water and organic solvents and disintegrate at a temperature exceeding 200 ° C.

The structure of the new substances is through elemental analysis and by the methods of IR spectroscopy and X-ray electron spectroscopy demonstrated.

For example, [N- (benzimidazolyl-2 -) - O- methylcarbamato] -zinc-ethylene-bis-dithiocarbamate a yellow Substance with a decomposition temperature of over 230 ° C.

[N- (Benzimidazolyl-2) -O-methylcarbamato] copper (II) ethylene bis-dithiocarbamate is a brown substance with a Decomposition temperature of over 200 ° C.

Di- [N- (benzimidazolylcarbamato] zinc ethylene bis-dithiocarbamate is a light yellow substance with a Decomposition temperature of over 280 ° C.

The specified connections are as follows produced.

The aqueous zinc mixture is placed in a reaction flask. or copper chloride solution and the aqueous suspension of N- (Benzimidazolyl-2) carbamic acid methyl ester. The Reaction material is at a temperature between 20 and 90 ° C Temperature mixed within 10 to 60 minutes. After Cooling of the reaction mixture is then the aqueous solution of Sodium ethylene bis-dithiocarbamate, made from aqueous Solution of ethylenediamine, carbon disulfide and sodium hydroxide solution, gradually added. The reaction takes place with thorough stirring at room temperature within 20 to 60 minutes. The The end product is isolated in a manner known per se.

The above compounds belong to the class of weakly toxic substances. When administered orally, LD ₅₀ exceeds 2000 mg / kg for rats.

The fungicidal properties of the invention Connections were made under different climates Vegetable, technical, melon, fruit and cereal crops (on 20 agricultural crops against 40 pathogens) checked.

Compounds 1 to 3 taken at a dose of 0.3 to 0.6 kg / ha, are highly effective and complex  Action against pathogens Erysiphales (the genus Sphaerotheca, Uncinula, Erysiphe), the family Peronosporaceae (of the genus Peronospora, Plasmopara, Pseudoperonospora) and the family Phytophthoraceae as well as against Puccinia graminis, Septoria graminum, Pseudopeziza trachiphila, Coniothyrium diplodiella and Botrytis cinerae on grapes, Fusarium oxysporum in pumpkin family, Monilia, polystigma, Coccomyces in fruit crops, Colletotrichum, Bacterium lachrymans, Fusarium oxysporum, Erysiphe in melon cultures and Bacterium Vesicatorium and Phytophthora infestans with tomatoes.

The fungicides according to the invention come primarily as Solutions, suspensions and wetting powder are used. The Active ingredient concentration of the mixtures is between 0.01 and 99.5 mass%. The mixture is made according to a conventional Process by mixing or grinding the inventive Complex salts with a carrier, for example with water, Acetone, ethanol, white carbon or kaolin. For the purpose of Production of the wetting powder is mixed by the inventive Compounds, mixture of polyethylene glycol acrylic esters, Sulfite waste liquor, white carbon or kaolin. For the purpose of The suspensions according to the invention are produced Compounds with a suitable solvent such as water, Mixed acetone or ethanol.

example 1

Place in a reaction flask equipped with a stirrer an aqueous solution of 6.8 g (0.05 mol) of zinc chloride and sets 9.55 g (0.05 mol) of N- (benzimidazolyl-2) - carbamic acid methyl ester as an aqueous suspension with intimate Stir to. The reaction mixture is mixed within 10 to 20 minutes and then sets an aqueous solution of Sodium ethylene bis-dithiocarbamate made from 4.3 g (0.05 mol) 70% ethylenediamine solution, 7.62 g (0.1 mol) Carbon disulfide and 4 g (0.1 mol) caustic soda in the form of a 10% water solution gradually. A light yellow arises Precipitation. Mixing will occur within 20 to 30  Minutes continued until an evenly colored suspension is formed. The precipitate is filtered off from Chlorine ions washed free and dried. 21.3 g are obtained (91% of theory) [N- (Benzimidazolyl-2) -O-methylcarbamato)] - zinc-ethylene-bis-dithiocarbamate with a decomposition temperature of over 230 ° C.

Found in%: C 33.59; H 3.34; N 14.99; Zn 15.3; C ₁₃ H ₁₅ N ₅ O ₂ S ₄ Zn

Calculated in%: C 33.41; H 3.24; N 14.99; Zn 13.99.

Example 2

In a reaction flask equipped with a stirrer, a reflux condenser and a thermometer, a solution of 17 g (0.1 mol) of CuCl ₂ .H ₂ O in 20 ml of water and a suspension of 19.1 g (0.1 Mol) N- (Benzimidazolyl-2) - carbamic acid methyl ester in 60 ml of water. The reaction mixture is stirred at a temperature of 50 ° C for 1 hour. After the reaction mixture has cooled to a temperature of 30 ° C., an aqueous solution of sodium ethylene bisdithiocarbamate, prepared from 8.6 g (0.1 mol) of 70% ethylenediamine solution, 8 g (0.2 mol) of caustic soda, is then added 50 ml of water and 15.2 g (0.2 mol) of carbon disulfide. The dark brown reaction mixture is mixed for 40 minutes at room temperature. The precipitate is filtered off and washed with water. 33 g (71.1% of theory) of [N- (benzimidazolyl-2) -O-methylcarbamato] copper (II) ethylene-bis-dithiocarbamate are obtained. The decomposition temperature exceeds 200 ° C.
Found in%: C 34.01; H 3.01; N 15.26; Cu 14.12; C ₁₃ H ₁₅ CuN ₅ O ₂ S ₄ .
Calculated in%: C 33.57; H 3.26; N 15.06; Cu 13.66.

Example 3

A solution of 5.5 g (0.04 mol) of zinc chloride in 50 ml of water is introduced into a reaction flask equipped with a reflux condenser, a stirrer and a thermometer and mixed with heating (90 to 95 ° C.) within 2 Hours with 11.5 g (0.06 mol) of N-benzimidazolyl-2-carbamic acid methyl ester (BMK). The reaction mixture is then cooled and filtered off. The precipitate is washed carefully with water, dried and recrystallized from acetonitrile. A complex compound of the composition (BMK) ₂ ZnCl ₂ of white color is obtained in a yield of 15 g (96.3% of theory) and with a melting point of 226 ° C.

The aqueous suspension of 10.4 g (0.02 mol) of the complex compound obtained is stirred with stirring, the aqueous solution of sodium ethylene bis-dithiocarbamate, prepared by reacting 1.7 g (0.02 mol) of 70% aqueous A solution of ethylenediamine, 3 g (0.04 mol) of carbon disulfide and 1.6 g (0.04 mol) of caustic soda in the form of a 10% strength aqueous solution were added. The reaction mixture is mixed at room temperature for 1 hour. The pale yellow precipitate obtained is filtered off, washed with water and dried. 12.7 g (96.2% of theory) of compound, di-N- (benzimidazolyl-2) -O-methylcarbamato-zinc-ethylene-bis-dithiocarbamate, are obtained with a decomposition temperature of 280% C.
Found in %. C 40.18; H 3.49; N 17.18; S 19.59; Zn 10.27; C ₂₂ H ₂₄ N ₈ O ₄ S ₄ Zn
Calculated in%. C 40.15; H 3.68; N 17.02, S 19.48; Zn 9.93.

 Example 4 Effect of the compounds on the mycelium of the fungal genera Fusarium moniliform, Aspergillus niger and Rhizoctonia solani.

The compounds are mixed with acetone and in the melted glucose potato agar (the temperature of the Medium is between 50 and 160 ° C) under sterile conditions placed in the Petri dishes before filling. 18 to 20 Hours after the medium is filled, the inoculation the agar plate. After the appropriate stop at a temperature of 25 to 26 ° C the diameter of the fungal colonies. The drug tests on Mycelium of the mushrooms occur at an active ingredient concentration of 0.003% using TMTD (tetramethylthiuram disulfide) as a comparison. The experiment was repeated three times.

The inhibition of mycelium growth is calculated according to Abbot's formula determined what
T is the growth inhibition of the culture in%, P _{k is} the diameter of colonies in the control culture, P _{o is} the diameter of culture colonies in the embodiment using the preparation.

The test results are shown in Table 1.

Table 1. Results obtained when testing the compounds on the mycelium of the fungi

Example 5 Effect of the compounds on the antiseptic Activity on the mycelium of pure fungal cultures, which is the destruction cause non-metallic materials, namely Aspergillus niger, Chaetomium globosum, paecilomuces varioti and Penicillium cyclopium

Method of determination of antiseptic activity of compounds 1 to 3 is that described above Try similar. Pentachlorophenol serves as a comparison. The Test results are given in Table 2.

Table 2. Results obtained when testing compounds for antiseptic activity

Example 6 Study the activity of compounds related to Erypsiphe of cucumber and wheat

The connections are tested in a greenhouse. The plants of cucumbers or wheat are sprayed with aqueous suspensions of the compounds to be tested in various concentrations of active substance and the control plants with water. After drying, the plants are artificially infected with the aqueous suspension of conidia Erysiphe cichoracearum and Erysiphe graminis (200,000 each 1 cm ^{3 of} water). The plants are kept in the greenhouse at a temperature of 20 to 25 ° C. The spread of the disease in the treated and control plants is estimated 10 days after their fungal attack. The wheat variety is red-grained ("Krasnosernaja"), the cucumber variety "Mnogoplodny VSChV" (BCXB). The experiments are repeated three times.

The test results are summarized in Table 3.

Table 3.

Example 7 Investigation of the effectiveness of compound 1 at fighting various fungi

Compound 1 against Botrytis gray rot cinerea is below at 0.05% active ingredient concentration Greenhouse conditions on beans (Russian black variety "Russkÿe Chernyje ") and grapes examined.

The plants grow until the formation of 7 to 10 leaves drawn.

The infection is carried out using the spore suspension of the fungus Botrytis cinerea grown on the carrot agar. The suspension density is 150,000-200,000 conidia / cm ³ . When examining the protective effect, the infection is carried out after 1 to 1.5 hours after the treatment of the plants with the compounds to be tested.

The infected plants are in a humidification chamber within 24 hours at a temperature of 26 ° C and 100% relative humidity. The fungal attack the plants will be on the 5th to 7th day after infection estimated. The test results are shown in Table 4.

Table 4. Fungicidal activity of the compounds against gray rot (botrytis cinerea) of beans and grapes

Example 8 Investigation of the effectiveness of compound 1 against Tomato powdery mildew (Phytophthora infestans)

Examination of the effectiveness of compound 1 against Tomato mildew is grown under the greenhouse conditions Tomato variety "Gribovskÿe" carried out. The infection takes place using those grown on potato slices Spore suspension of the fungus Phytophthora infestans.

When examining the protective effect, one takes the Infection after 1.5 to 2 hours before. The infected plants would be in a humidification chamber for 24 hours a temperature of 18 ° C and 100% relative humidity held.

The fungus infestation on the 4th and 5th day after the contagion estimated.

The test results are shown in Table 5.

Table 5. The effectiveness of Compound 1 against tomato powdery mildew (Phytophtora infestans)

Example 9 Investigation of the effectiveness of compound 2 at  combating tomato powdery mildew (Phytophthora infestans)

The Effectiveness of Compound 2 on Plants of "Gribovskii" tomatoes examined. The plants are treated with the preparation and then with the aqueous suspension of conidia spores of the fungus Phytophthora infestans artificially infected. The spore concentration the suspension is 50,000 per 1 ml of water. The Conidia suspension will leak before inoculation Keep zoospores at 10 ° C for 40 minutes. After inoculation you put the plants in a humidification chamber at a temperature between 20 and 22 ° C for 24 hours a day. After 6 days, the disease level is determined of leaves. The evaluation is based on a sense of proportion in the Five point procedure. The experiments are repeated three times.

Zineb, N, N'-zinc-ethylene-bis-dithiocarbamate serves as a comparison.

The test results are given in Table 6.

When testing the preparation to combat Tomato powdery mildew in the field trial (Moscow region) Plant twice during the growing season Compound 2 treated. The first spraying of plants with the preparation is made before the illness and the second after 14 days. Serves as a comparison Polycabazin, double salt of zinc N-N'-ethylene-bis-dithiocarbamate and ethylene bis (thiocarbamoyl) disulfide. The attempts are repeated three times. The test results are in the table 6 cited.

Table 6. Test results obtained in combating tomato powdery mildew (Phytophthora infestans)

Example 10 Compound 3 tests on the mycelium of fungi, pathogens of potato Fusarium sambucinum, Sphaeropsis malorum and Rhizoctonia solani.

The methodology of tests on compound 3 is that of Experiment on the mycelium of phytopathogenic fungi Fusarium moniliforme and Aspergillus niger, only that the preparations do not ins Glucose-potato medium but introduced into the wort agar medium will.

The test results are shown in Table 7.  

Table 7 Results obtained when testing preparations against potato pathogens

Example 11 Investigation of the effectiveness of the invention Compounds to control wheat and Currant diseases

When examining the effect of the compounds for The plants were combating wheat diseases twice sprayed with fungicides during the growing season. The plants were sprayed with the preparations for the first time in the tillage stage of wheat and the second at the stalk formation. The experiments are repeated three times.

In the course of the action of the compounds to combat The bushes became from diseases of the black currant the fruiting black currant while treated twice with fungicides during the growing season. The black currant was first sprayed before Flowering and the second performed after harvest. The attempts are repeated three times.

The test results are shown in Table 8.  

Table 8. Effectiveness of the compounds against diseases of wheat and black currant

Example 12 Effectiveness of the compounds according to the invention against Piricularia patch disease of rice (Piricularia oryzae)

The effectiveness of compound 1 against Piricularia Spotted disease of rice (Piricularia oryzae) is found under greenhouse conditions examined on the variety "Dubowski". The plants are grown in pots up to the stage of formation from 3 to 4 Sheets raised.

The infection is carried out using the spore suspension of the mushroom Piricularia oryzae grown on the carrot agar. The suspension density is 150,000 to 200,000 conidia per 1 cm ³ . When examining the protective effect, the infection is carried out 1.5 to 2 hours after the treatment of the plants with fungicides. The infected plants are kept in a humidification chamber over a period of 24 hours at 26 ° C and a relative humidity of 100 ° C. Plant infestation is estimated on the 7th to 10th day of infection.

The test data are shown in Table 9.  

Table 9. Effectiveness of preparations against Piricularia spot disease in rice (Piricularia oryzae)

Example 13 Investigation of the effectiveness of compound 2 on potato plants (in field trial)

In the course of the study of the activity of compound 2 against potato herb blight (Phytophthora infestans) the plants three times during the growing season with fungicides splattered. The first injection takes place before the illness, and the following injections will be after 12 up to 14 days. A mixture serves as a comparison from 15% zinc-ethylene-bis-dithiocarbamate and from 65% Copper (II) oxychloride exists. The potato variety is called "Ogonjok". The attempt is repeated three times. The test results are summarized in Table 10.

The table shows that compound 2 with Comparison level is effective.  

Table 10, results obtained when testing compound 2 for controlling potato blight (Phytophthora infestans)

Example 14 Investigation of the fungicidal activity of compound 3 on pure mushroom cultures

Pure cultures grown on potato dextrose agar the fungus as a causative agent of the pythium fruit rot in cucumbers (Pythium sp.), The sugar beet root rot, the salad rot (Bremia sp.), The Phytophthora blotch from Tomatoes (Phytophthora infestans), the gray rot of strawberry (Botrytis cinerea), the sclerotinia rot of the sunflower (Sclerotinia sclerotiorum), the blight in potatoes (Phoma sp.) And Fusarium rot in cucumbers (Fusarium sp.) were taken as test objects.

The investigation of fungicidal activity is carried out in the Way carried out that the acetone suspensions of the preparation are introduced into the agarated medium. The inhibition of growth of mushroom conidia is on the 6th day according to the formula of Abbott estimated.

The test results (Table 11) suggest that the compound 3 the N- (benzimidazolyl-2) -carbamic acid methyl ester in the activity against the named test objects (the Mushrooms belong to the class of lower mushrooms) and superior  Zinc-ethylene-bis-dithiocarbamate is practically equivalent. In addition, compound 3 is active against fungi, against the N- (benzimidazolyl-2) -carbamic acid methyl ester are sensitive, this preparation not worse, at it is superior to individual mushrooms. Confirm the information obtained the advantage of compound 3, which has fungicidal activity both against lower fungi (Table 11, Experiment 1) as also against imperfecti fungi (higher fungi, Table 11, Experiment 2) has.

Table 11. Results obtained when testing the new compound 3 on pure cultures

Examination of fungicidal activity against Erysiphe cichoracearum and Erysiphe graminis and Phytophthora infestans with tomatoes and potatoes has shown that the Compounds according to the invention have a high fungicidal activity which of the comparisons, namely Karathan for Control of Erysiphe cichoracearum and Zineb as a preparation against Phytophthora infestans. The tested connections have a significantly broader spectrum of effects the comparative preparations (zinc-ethylene-bis-dithiocarbamate, TMTD and pentachlorophenol). The connections are very effective against complexes of pathogens in various agricultural crops including Peronosporaceae and Erysiphales. Zinc-ethylene-bis-dithiocarbamate and TMTD are not effective and for use in agriculture against Erysiphales different plants not allowed. Karathan is only active against Erysiphales and against Peronosporaceae different agricultural crops not effective. Pentachlorophenol is known as an antiseptic and as a fungicide to combat diseases of agricultural Cultures not applicable.

The use of the compounds according to the invention simultaneously to combat Peronosporaceae and Erysiphales different agricultural crops becomes Reduction in the number of processes and consumption standards of the preparation and to reduce environmental pollution to lead.

Example of the production of wetting powder

The effectiveness of preparations is in the fight different diseases of agricultural crops. The plants are sprayed using an aqueous spray Suspension prepared from a wetting powder a consumption standard between 500 and 600 l / h Working fluid.

50 parts by weight are used to produce the wetting powder the compound of the invention, 3 parts by weight Mixture of polyethylene glycol acrylic esters, 3 parts by weight Sulfite waste liquor, 10 parts by weight of white carbon and 34 parts by weight Kaolin and mixed until a homogeneous mixture is formed.

Claims (6)

1. Zinc and copper complex salts of ethylene-bis-dithiocarbamic acid and N- (benzimidazolyl-2) -carbamic acid methyl ester of the general formula where M stands for zinc when n = 1 or 2 or for copper when n = 1. 2. [N- (Benzimidazolyl-2 -) - O-methylcarbamato] zinc-ethylene bis-dithiocarbamate according to claim 1 of the formula 3. [N- (Benzimidazolyl-2) -O-methylcarbamato] copper (II) - ethylene-bis-dithiocarbamate according to claim 1 of the formula 4. Di- [N- (benzimidazolyl-2) -O-methylcarbamato] zinc ethylene bis-dithiocarbamate according to claim 1 of the formula 5. A process for the preparation of the compounds according to claim 1 to 4, characterized in that the copper or zinc chloride with N- (benzimidazolyl-2) - carbamic acid methyl ester in an aqueous medium at a temperature between 20 and 90 ° C with subsequent Add sodium ethylene bis-dithiocarbamate is implemented. 6. Fungicidal mixture which contains an active ingredient and a filler, characterized in that it contains zinc and copper complex salts of ethylene-bis-dithiocabamic acid and N- (benzimidazolyl-2) - carbamic acid methyl ester as claimed in claims 1 to 4 at the following ratio as the active ingredient % of the constituents mentioned contains:
Active ingredient 0.01 to 99.05
Filler up to 100.